Bis(dicyanamido-κN)[tris­(3-amino­propyl)amine-κ4 N]nickel(II)

Jun Luo; Xin-Rong Zhang; Li-Juan Qiu; Feng Yang; Bao-Shu Liu

doi:10.1107/S1600536813015651

. 2013 Jun 15;69(Pt 7):m385–m386. doi: 10.1107/S1600536813015651

Bis(dicyanamido-κN)[tris(3-aminopropyl)amine-κ⁴ N]nickel(II)

Jun Luo ^a, Xin-Rong Zhang ^a, Li-Juan Qiu ^a, Feng Yang ^a, Bao-Shu Liu ^a,^*

PMCID: PMC3772421 PMID: 24046564

Abstract

In the title complex, [Ni(C₂N₃)₂(C₉H₂₄N₄)], the Ni^II atom is coordinated in a distorted octahedral geometry by one tris(3-aminopropyl)amine (trisapa) ligand and two dicyanamide (dca) ligands [one of them disordered in a 0.681 (19):0319 (19) ratio]. Intermolecular N—H⋯N hydrogen bonds involving the N atoms of the dca anions and the trisapa amine H atoms result in the formation of a three-dimensional network.

Related literature

For magnetic properties and structural types of dicyanamide complexes, see: Batten (2005 ▶); Batten & Murray (2003 ▶); Batten et al. (1998 ▶); Ghosh et al. (2011 ▶); Ion et al. (2013 ▶); Manson et al. (1999 ▶); Mastropietro et al. (2013 ▶); Turner et al. (2011 ▶). For dicyanamide complexes with multidentate Schiff bases, see: Sadhukhan et al. (2011 ▶); Fondo et al. (2011 ▶); Bhar et al. (2011 ▶). For dicyanamide complexes with polyamines as co-ligands, see: Khan et al. (2011 ▶). For Ni—N bond lengths in aliphatic amine nickel complexes, see: Cho et al. (2002 ▶); Brezina et al. (1999 ▶) and in [Ni(tn)₂{C₂N₃}](ClO₄)(tn is trimethylenediamine, see: Li et al. (2002 ▶).

Experimental

Crystal data

[Ni(C₂N₃)₂(C₉H₂₄N₄)]
M _r = 379.13
Monoclinic,
a = 10.171 (1) Å
b = 11.3960 (11) Å
c = 15.5305 (15) Å
β = 105.660 (2)°
V = 1733.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.14 mm⁻¹
T = 213 K
0.17 × 0.09 × 0.05 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.830, T _max = 0.945
12722 measured reflections
4056 independent reflections
3403 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.079
S = 1.07
4056 reflections
269 parameters
20 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813015651/bg2508sup1.cif

e-69-0m385-sup1.cif^{(20.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813015651/bg2508Isup2.hkl

e-69-0m385-Isup2.hkl^{(198.8KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2C⋯N10ⁱ	0.92 (2)	2.38 (2)	3.255 (2)	160 (2)
N2—H2D⋯N10ⁱⁱ	0.80 (2)	2.43 (2)	3.193 (2)	158 (2)
N3—H3D⋯N10ⁱ	0.90 (2)	2.36 (2)	3.154 (2)	148 (2)
N4—H4D⋯N7ⁱⁱⁱ	0.90 (3)	2.19 (3)	3.094 (3)	176 (2)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

This project was supported by the National Natural Science Foundation of China. (NSFC 20571086).

supplementary crystallographic information

Comment

Recently, dicyanamide complexes have attracted considerable interest because of their fascinating magnetic properties and diverse structural types (Turner et al., 2011; Batten et al., 2005; Batten et al., 2003). For example, the binary transition metal dicyanamide complexes display long-range magnetic ordering, with the nature of the ordering dependent on the particular metal ion involved. Thus the Cr (47 K) and Mn (16 K) compounds are antiferromagnets (Manson et al., 1999), while the Co (9 K) and Ni systems (21 K) are ferromagents (Batten et al., 1998). It is well known that the structure and the magnetic property of the complexes are related to the nature of the co-ligands (Ghosh et al., 2011; Mastropietro et al., 2013; Ion et al., 2013). Although a great effort is focused on studies of dicyanamide complexes with multidentate schiff bases (Sadhukhan et al., 2011; Fondo et al., 2011; Bhar et al., 2011), few dicyanamide complexes with polyamines as co-ligands have been reported recently (Khan et al., 2011). To further study the effect of the nature of co-ligands on the structures and properties of dicyanamide complexes, we herein report the synthesis and crystal structure of the title new nickel dicyanamide complex [Ni(trisapa)(C₂N₃)₂] (I).

The nickel ion in I is coordinated by four N atoms from the tris(3-aminopropyl) amine and two terminal N atoms from two dicyanamide anions to form a distorted octahedral geometry, in which the equatorial plane is formed by the three N atoms(N2, N3, N4) of tris(3-aminopropyl)amine and one nitrile N atom (N8) of a monodentate (disordered) dicyanamide, where the disorder atoms are C12 and C12', N9 and N9', C13 and C13' respectively. The two apical sites are occupied by one trisapa N atom(N1) and one nitrile N atom (N5) of another monodentate dicyanamide (Fig. 1). Table. 2 shows the intermolecular hydrogen interactions between the uncoordinated N atoms of dicyanamide anions and the amine H atoms of trisapa, responsible of the construction of a three-dimensional network (Fig. 2). The Ni—N (trisapa) distances (2.100 (2)–2.196 (1) Å) are rather different, with values similar to the corresponding distances in the aliphatic amine nickel complexes (Cho et al., 2002; Brezina et al., 1999). The apical Ni—N (dicyanamide) distance(2.145 (1) Å) is slightly longer than the basal Ni—N(dicyanamide) distance(2.090 (2) Å). These distances in I are comparable to the corresponding ones in [Ni(tn)₂{C₂N₃}](ClO₄)(tn is trimethylenediamine, Li et al., 2002). In I, N—Ni—N cis angles range from 89.36 (7)° to 90.37 (6)° (basal-basal) and 84.32 (6)° to 95.61 (6)° (basal-apical), indicating that the distortion from an ideal octahedral geometry in I is not serious.

Experimental

A 4 ml ethanol solution of tris(3-aminopropyl)amine(0.10 mmol, 18.83 mg) and a 4 ml e thanol solution of nickel nitrate(0.10 mmol, 29.08 mg) were mixed and stirred for 5 min, the mixed solution was pale-blue. To the mixture was added a 2 ml aqueous solution of sodium dicyanamide (0.20 mmol, 17.81 mg). After stirred for another 5 min, the solution was filtered and the filtrate was slowly evaporated in air. After one week, blue block crystals of I were isolated in 34% yield. Anal: Calculated for C13H24N10Ni: C 41.18%, H 6.38%, N 36.95%. Found C 40.86%, H 6.47%, N 37.07%.